US3641196A - Stabilizing polyacetals - Google Patents

Stabilizing polyacetals Download PDF

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Publication number
US3641196A
US3641196A US818116A US3641196DA US3641196A US 3641196 A US3641196 A US 3641196A US 818116 A US818116 A US 818116A US 3641196D A US3641196D A US 3641196DA US 3641196 A US3641196 A US 3641196A
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polyacetals
formaldehyde
component
polycondensate
stabilizing
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US818116A
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Bruno Sander
Franz Schmidt
Heinrich Sperber
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
    • C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen

Definitions

  • Known polyacetals of this type include macromolecular polymers of formaldehyde and trioxane, for example those whose terminal hydroxyl groups have been stabilized by chemical reaction such as by etherification or esteri fication, and particularly macromolecular copolymers of trioxane with from 0101 to 20 mole percent, especially from 0.1 to mole percent, of the total monomers of copolymerizable compounds which introduce recurring alkylene and particularly oxyalkylene units having at least two and preferably from two to four adjacent carbon atoms into the polymer chain, for example with appropriately constituted cyclic acetals or cyclic ethers, particularly having from three to eight carbon atoms such as ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 2-methoxymethyldioxolane, butanediol-1,4-formal or diglycolformal, or with linear polyacetals having recurring acetal groups in the main molecular chain such
  • polyacetals of this type can be stabilized against thermal degradation such as may take place in the conventional processing of the polyacetals as thermoplastics, by adding certain organic compounds of nitro gen-Examples of prior art stabilizers are amides, polyamides, urea, thiourea, hydrazines, hydrazides, aromatic nitro compounds or polycondensation products of N,N'- dimethyoldiamides of dicarboxylic acids and cyclic N,N'- alkylen'ur' eas.
  • thermoplastic polyacetals whose recurring units ofthemain molecular chain consist to the extent of at least 80 mole percent of oxymethylene units can be stabilized against the action of heat using up to 5% by weight of'the amount of polyacetal of a compound containing an amide group, with or Without a conventional antioxidant, while avoiding the said disadvantages, by using as the compound containing an amide group for stabilizing the polyacetal a polycondensate which has been prepared by polycondensation of:
  • the molar ratio of the components (A), (B) and (C) can be varied within wide limits; the molar ratio of (D) to the sum of the components (A), (B) and (C) should however be from 1:1 to 1.5: 1.
  • diamides of dicarboxylic acids having from four to eighteen and particularly from five to twelve carbon atoms are the diamides of azelaic acid, sebacic acid, decanedicarboxylic acid or dimethylsuberic acid; adipamide and isophthalamide in particular are very suitable.
  • Preferred components (B) are amides having at least two and particularly from two to four amide groups and at least one basic secondary or tertiary nitrogen atom in the aor B-position to at least one amide group in the molecule.
  • Products such as are obtained by reaction of glycidamide with appropriate amounts of ammonia, primary monamines or primary or secondary diamines, particularly with C -C -alkylenediamines, with piperazine or With imidazolidine are particularly suitable.
  • nitrilotrilactamide iminodilactam- 40 ide, ethylenediamine N,N,N',N' tetralactamide, hexamethylenediamine-N,N,N',N'-tetralactamide, piperazine- N,N-lactamide and imidazolidine-1,3-dilactamide.
  • nitrilotriacetamide iminodiacetamide
  • nitrilotripropionamide iminodipropanamide
  • piperazine N,N dipropionamide and imidazolidine-1,3- dipropionamide imidazolidine-1,3- dipropionamide.
  • N,N'-alkylenureas having from three to ten carbon atoms which are preferred as component (C) are N,N'-ethylenurea and N,N'propylurea, and the alkylene groupings may bear alkoxy, alkyl or hydroxyl groups for example is substituents, such as in the case of 4-methoxy-5,5-dimethyl-N,N-propyleneurea or 4-hydroxy 5,5 dimethyl '6 isopropyl N,N' propylenurea.
  • N,N'-disubstituted ureas having alkyl, aryl and/or aralkyl radicals having one to eight carbon atoms, particularly hydrocarbon radicals, as substituents are N,N-dialkylureas such as N,N'-dimethylurea, N,N' diethylurea or N,N-dibutylurea, and also N,N'-diarylureas and N,N-aralkylureas such as N,N'-diphenylurea or N,N'-ditolylurea, and N-alkyl-Narylureas such as N-methyl-N'-tolylurea.
  • N,N-dialkylureas such as N,N'-dimethylurea, N,N' diethylurea or N,N-dibutylurea
  • N,N'-diarylureas and N,N-aralkylureas
  • formaldehyde as component (D) (preferably in aqueous solution) for the production of the polycondensates to be used according to this invention
  • conventionally employed substances which yield formaldehyde such as paraformaldehyde, trioxane or polyoxymethylene, may be used in appropriate amounts.
  • formaldehyde in the form of N-methylol compounds of components (A) and/or (C) prepared in a preliminary stage.
  • the amount of formaldehyde (in free or combined form) is advantageously chosen so that the molar ratio of formaldehyde (component (D)) to the sum of components (A), (B) and (C) is from about 1:1 to 1:1.5:1, i.e. about 1 to 1.5 molecules of formaldehyde is present for each two amide groups in the components (A), (B) and (C).
  • 1 mole of isophthalamide (A) is polycondensed with about 0.5 to 0.7 mole of component (B), 1 mole of component (C) and from about 2.6 to 2.8 moles of formaldehyde (D). It is preferred to use component (B) in a molar ratio of from 0.2 to 0.8 mole to 2 moles of the sum of the components (A) and (C).
  • Polycondensation catalysts conventionally used in aminoplast chemistry are suitable as acid polycondensation catalysts in the production of the polycondensates to be used according to this invention, in the conventional amounts, especially mineral acids such as sulfuric acid or phosphoric acid in an amount of from about 0.05 to 0.5% of the weight of components (A), (B), (C) and (D).
  • the aqueous polycondensate After polycondensation in aqueous medium at from about 50 to 100 C., particularly from 80 to 100 C. (which generally is over after about one to three hours) the aqueous polycondensate is advantageously adjusted to a pH of from 7 to 7.5 by adding alkali and thus rendered free from acid. It has proved to be advantageous to separate the polycondensate (which usually separates as a viscous layer containing some water) from the aqueous layer, to add aqueous alkali solution and wash it. When the water-containing polycondensate layer has a high viscosity it is often advantageous to add an organic solvent which is miscible with water such as 1,3-dioxolane or methanol.
  • the polycondensate may be added in the form of such solutions to the polyacetal to be stabilized; usually it is advantageous however previously to isolate the polycondensate in solid form by a conventional method. Isolation of the polycondensate in solid form may take place particularly advantageously by spray-drying solutions or suspensions of acid-free Water-containing polycondensate in a heated stream of inert gas, so that the condensate is obtained as a fine powder practically de void of uncombined formaldehyde and water.
  • Particularly suitable condensates generall have K values of from 14 to 18 and melt at from about 110 to 180 C.
  • Phenolic antioxidants such as C to C alkyl-substituted phenols and alkylenebisphenols, for example 2,2- methylene-bis-(4-ethyl-6-tert-butylpehnol), 2,6 ditert-butyl p cresol, 2,2 methylene-bis-(4-methyl 6 tert-butylphenol) or 2,2'-butylidene-bis-(4 methyI-G-tert-butylphenol) are preferred.
  • Hydrazones such as benzaldehyde- (a-N-methyl)-phenylhydrazone, piperonal-(a N-methylphenylhydrazone, 3,5-ditert-butyl-4-hydroxybenzaldehyde- (a-N-methylphenylhydrazone) and mixtures of the said compounds are also very suitable.
  • Stabilizers to be used according to this invention can be readily incorporated into the polyacetals, either in conventional dry mixers into the powdered polyacetals with or without pigments, fillers, plasticizers, lubricants and the like, or in the solid or dissolved condition into molten polyacetals.
  • the stabilizers may be added to the copolymers present as powder or granules after removal of the unstable constituents, for example by hydrolytic or thermal degradation, and then incorporated by melting and homogenization.
  • the stabilizers used according to this invention which are incorporated in amounts of up to by weight, usually from 0.1 to 2% by weight and particularl from 0.1 to 1% by weight into the polyacetals to be stabilized result in particularly good stabilizing effects.
  • the stabilized polyacetals according to this invention may be repeatedly processed from the melt without becoming discolored. They are particularly suitable for the production of moldings such as are used in industry.
  • Polyacetals having at least mole percent of oxymethylene (--O--CH units in the main molecular chain which can be stabilized according to this invention include particularly high molecular weight thermoplastic oxymethylene polymers which have been prepared by polymerization of formaldehyde or trioxane and 'whose terminal groups are protected, for example esterified or etherified, and especially oxymethylene copolymers which (besides 80 to 99.5 mole percent of oxymethylene groups) have 0.5 to 20 and particularly 0.5 to 5 mole percent of alkylene groups and particularly oxyalkylene groups having at least two and particularly from two to four adjacent carbon atoms in the main molecular chain.
  • trioxane may be prepared for example by copolymerization of trioxane with cyclic acetals or ethers having preferably three to eight ring atoms such as ethylene oxide, 1,3-dioxolane, 1,3-dioxane, butanediolformal'or diethylene glycolformal, or polyacetals such as polydioxolane, or olefinically unsaturated compounds such as isobutylene or norbornadiene, in the presence of cationic catalysts.
  • cyclic acetals or ethers having preferably three to eight ring atoms such as ethylene oxide, 1,3-dioxolane, 1,3-dioxane, butanediolformal'or diethylene glycolformal, or polyacetals such as polydioxolane, or olefinically unsaturated compounds such as isobutylene or norbornadiene, in the presence of cationic catalysts
  • the mixture is heated to from to C. while stirring and condensed for ninety minutes under slight reflux, two liquid layers being slowly formed.
  • the upper aqueous layer is siphoned ofi and discarded.
  • the lower condensate layer is stirred with water and, after the freshly formed upper aqueous layer has also been siphoned 01f, adjusted to a pH value of 7.1 with dilute caustic soda solution.
  • the layer with the condensate contains about 50% of solids and has a viscosity of from 1 to centipoises at 20 C.
  • the polycondensate is recovered in the form of a fine powder from the neutral polycondensate layer by spray drying in a steam of heated inert gas.
  • the polycondensate has a K value of 16 to 17 and melts at from 150 to 155 C.
  • the neutralized layer containing the polycondensate is spray-dried.
  • a colorless powdery product is obtained having a K value of 16.9 and a softening point of from to 140 C.
  • a polycondensate having a K value of 15.8 and a softening point of from to C. is obtained from the neutralized layer containing the polycondensate b drying in vacuo.
  • the extruded polyacetal resin is tested for colorlessness.
  • the stability of the molding material obtained is measured by determining the loss in weight after heating a sample at 222 C. while passing nitrogen or air over it. The results are given in the following table.
  • thermoplastic polyacetals Whose recurring units in the main molecular chain consist to the extent of at least 80 mole percent of oxymethylene (CH units which comprises adding to the polyacetal a stabilizing amount in the range of 0.1 to by weight of the weight of the polyacetal of a polycondensate which has been prepared by polycondensation for about 1-3 hours in an acid aqueous medium at from about 40 to 100 C. of:
  • N,N-alkylenurea having from three to ten carbon atoms and/or a N,N'-disubstituted urea having an alkyl, aryl or aralkyl radical having from one to eight carbon atoms as substituents;
  • component (A) is adipamide.
  • component (A) is isophthalamide.
  • component (B) is nitrilolactamide.
  • component (C) is N,N'-ethylenurea.
  • component (C) is N,N'-propylenurea.
  • component (D) is an aqueous solution of formaldehyde.
  • component (D) is a substance which will yield formaldehyde.
  • component (A) is isophthalamide and the molar ratio of components (A), (B), (C) and (D) is 1:0.50.7:1:2.6-2.8.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
US818116A 1968-04-25 1969-04-21 Stabilizing polyacetals Expired - Lifetime US3641196A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1769243A DE1769243C2 (de) 1968-04-25 1968-04-25 Verfahren zum Stabilisieren von PoIyacetalen

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US (1) US3641196A (enExample)
BE (1) BE731645A (enExample)
DE (1) DE1769243C2 (enExample)
FR (1) FR2006884A1 (enExample)
GB (1) GB1255546A (enExample)
NL (1) NL6906285A (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139575A (en) * 1975-09-10 1979-02-13 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Polyoxymethylene molding composition containing melamine formaldehyde polycondensate
US4363906A (en) * 1980-04-03 1982-12-14 Montedison S.P.A. Condensation product prepared from N,N'-ethylene-urea and formaldehyde

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4811217B1 (enExample) * 1970-05-28 1973-04-11

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139575A (en) * 1975-09-10 1979-02-13 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Polyoxymethylene molding composition containing melamine formaldehyde polycondensate
US4230606A (en) * 1975-09-10 1980-10-28 Deutsche Gold -Und Silber-Scheidearstalt Vormals Roessler Polyoxymethylene molding composition containing melamine formaldehyde polycondensate
US4363906A (en) * 1980-04-03 1982-12-14 Montedison S.P.A. Condensation product prepared from N,N'-ethylene-urea and formaldehyde

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GB1255546A (en) 1971-12-01
BE731645A (enExample) 1969-10-17
NL6906285A (enExample) 1969-10-28
DE1769243C2 (de) 1975-05-07
DE1769243B1 (de) 1971-02-11
FR2006884A1 (enExample) 1970-01-02

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